WO2005092976A1 - Polyols proteges par du cetal destines a des revetements a faible teneur en contaminant organique volatil (cov) - Google Patents

Polyols proteges par du cetal destines a des revetements a faible teneur en contaminant organique volatil (cov) Download PDF

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Publication number
WO2005092976A1
WO2005092976A1 PCT/US2005/008888 US2005008888W WO2005092976A1 WO 2005092976 A1 WO2005092976 A1 WO 2005092976A1 US 2005008888 W US2005008888 W US 2005008888W WO 2005092976 A1 WO2005092976 A1 WO 2005092976A1
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Prior art keywords
carbon atoms
meth
poly
acrylate
coating composition
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PCT/US2005/008888
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English (en)
Inventor
Robert Barsotti
Laura Lewin
Alexei A. Gridnev
Original Assignee
E.I. Dupont De Nemours And Company
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Priority to EP05725807A priority Critical patent/EP1727862A1/fr
Publication of WO2005092976A1 publication Critical patent/WO2005092976A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
    • C08G18/3825—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing amide groups
    • C08G18/3827—Bicyclic amide acetals and derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C08L2666/20—Macromolecular compounds having nitrogen in the main chain according to C08L75/00 - C08L79/00; Derivatives thereof

Definitions

  • VOC low volatile organic compounds
  • These coatings are predominantly solvent based and use hydroxyl/isocyanate curing.
  • One component of the system contains the hydroxyl functional species; the other component contains the isocyanate.
  • These components are mixed just prior to spraying on the vehicle.
  • These two-part coatings need to remain at a low enough viscosity to allow for spraying over an extended timeframe and then, after spraying, require rapid curing to a three- il'" " I ,: G i- ⁇ Wlsif ⁇ ?larif , vehicle to maximize productivity and physical properties.
  • the original coating in and around the damaged area is typically sanded or ground out 5 by mechanical means.
  • the original coating is stripped off from a portion or off the entire auto body to expose the bare metal underneath.
  • the repaired surface is coated, preferably with low VOC coating compositions, typically in portable or permanent low cost painting enclosures vented to atmosphere to remove the organic solvents 0 from the freshly applied paint coatings in a safe manner from the standpoint of operator health and explosion hazard.
  • the drying and curing of the freshly applied paint takes place within these enclosures.
  • the foregoing drying and curing steps take place within the enclosure to prevent the wet paint from collecting dirt in the air or other 5 contaminants. As these paint enclosures take up significant floor space of typical small auto body paint repair shops, these shops prefer to dry and cure these paints as fast as possible.
  • JP 2001-163922 describes reacting an oligomer comprising a polyorthoester, either an alpha- or beta-glycol, and an ethylenic0 unsaturated group with a resin having at least two hydroxyl groups.
  • WO 02/057339 describes protecting hydroxyl groups through the use of spiroorthocarbonate groups.
  • U.S. Patent No. 6,297,329 issued to van den Berg et al. on October 2, 2001 , discloses a coating composition comprising a first compound comprising at least one bicyclo- or spiro- 5 orthoester group and a second compound comprising at least two hydroxyl-reactive groups.
  • U.S. Patent No. 6,045,870 issued to Noura et al.
  • the coatings disclosed herein are stable under anhydrous conditions but become active, or deblock, after application via the absorption of atmospheric moisture, which will release the initial hydroxyl groups. Once the hydroxyl group is released, it will quickly react with the isocyanate cross-linker to develop a5 three-dimensional network, and very rapid film formation will occur.
  • ketal groups block the hydroxyl groups of the poly(meth)acrylate.
  • the ketal groups can be removed through hydrolysis in order to facilitate cross-linking through0 reaction with polyisocyanate compounds.
  • the invention also relates to a process for curing the aforementioned coating composition.
  • the invention also relates to a process for coating substrates wherein a clear coat comprising the aforementioned coating composition is coated over a base coat.
  • the invention also relates to a process for blocking the hydroxyl compound through reaction with a ketal compound.
  • low VOC coating composition means a coating composition that includes the range of from 0.1 kilograms (1.0 pounds per gallon) to 0.72 kilograms (6.0 pounds per gallon), preferably 0.3 kilograms (2.6 pounds per gallon) to 0.6 kilograms (5.0 pounds per gallon), and more preferably 0.34 kilograms (2.8 pounds per gallon) to 0.53 kilograms (4.4 pounds per gallon) of the solvent per liter of the coating composition. All VOCs are determined under the procedure provided in ASTM D3960.
  • the present invention concerns a coating composition comprising a poly(meth)acrylate containing at least two hydroxyl groups blocked by hydrolyzable ketal groups and at least one polyisocyanate compound.
  • the invention concerns a process for blocking the hydroxyl groups of poly(meth)acrylates comprising thermally reacting a poly(meth)acrylate containing at least two hydroxyl groups with at least one vinyl ether compound.
  • blocked is meant forming a hydrolyzable ester through reaction between at least two hydroxyl groups of a poly(meth)acrylate and at least one vinyl ether compound to form hydrolyzable ketal groups.
  • a vinyl ether compound blocks substantially all of the hydroxyl groups.
  • coating compositions are formulated by first taking a poly(meth)acrylate compound containing at least two hydroxyl groups and protecting the hydroxyl groups through an acid catalysis reaction with at least one vinyl ether compound.
  • the etherification0 reaction results in a poly(meth)acrylate compound wherein at least two hydroxyl groups have been blocked by ketal groups.
  • the blocked poly(meth)acrylate compound is unblocked by hydrolyzing the ketal groups with water, optionally in the presence of an acid catalyst, either prior to or simultaneously with the5 addition of a polyisocyanate compound.
  • the unblocked hydroxyl groups of the poly(meth)acrylate compound can freely react with the polyisocyanate compound to produce coating compositions by any method known to one of ordinary skill in the art.
  • Non-limiting examples of poly(meth)acrylates used in the coating0 composition are polymerized monomers of acrylic and methacrylic acid esters of straight-chain or branched monoalcohols of 1 to 20 carbon atoms.
  • Preferred esters are alkyl acrylates and methacrylates having 1 to 12 carbons in the alkyl group such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, pentyl acrylate, hexyl5 acrylate, 2-ethyl hexyl acrylate, nonyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, 2-ethyl hexyl methacrylate, nonyl methacrylate, lauryl methacrylate, and the like.
  • Isobomyl methacrylate and isobornyl acrylate monomers can be0 used.
  • Cycloaliphatic (meth)acrylates can be used such as trimethylcyclohexyl acrylate, t-butyl cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-ethylhexyl methacrylate, and the like.
  • Aryl acrylates and methacrylates such as benzyl acrylate and benzyl methacrylate also can be used. i if, " ⁇ * 'I!
  • Suitable monomers include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyisopropyl acrylate, 2,3-dihydroxypropyl acrylate, hydroxybutyl acrylate, dihydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyisopropyl methacrylate, hydroxybutyl methacrylate, dihydroxypropyl methacrylate, dihydroxybutyl methacrylate and the like, and mixtures thereof. Hydroxy functionality may also be obtained from monomer precursors, for example, the epoxy group of a glycidyl methacrylate unit in a polymer.
  • Such an epoxy group may be converted, in a post polymerization reaction with water or a small amount of acid, to a hydroxy group.
  • Suitable other olefinically unsaturated comonomers that can be used include acrylamide and methacrylamide and derivatives such as alkoxy methyl (meth) acrylamide monomers, such as methacrylamide, N- isobutoxymethyl methacrylamide, and N-methylol methacrylamide; maleic, itaconic, and fumaric anhydride and its half and diesters; vinyl aromatics such as styrene, alpha methyl styrene, and vinyl toluene; and polyethylene glycol monoacrylates and monomethacrylates.
  • the M n of the poly(meth)acrylate is in the range of from about 200 to about 50,000. More preferably, the M n of the poly(meth)acrylate is in the range of from about 300 to about 20,000. Even more preferably, the M n of the poly(meth)acrylate is in the range of from about 500 to about 6,000. All molecular weights referred to herein •P" chromatography ("GPC") using a polystyrene standard.
  • the poly(meth)acrylate preferably includes in the range from 2 to 200, more preferably in the range from 2 to 50, and most preferably in the 5 range from 2 to 20 hydroxyl groups per poly(meth)acrylate compound.
  • the poly(meth)acrylate has a polydispersity in the range of from about 1.5 to about 10.0. In a more preferred embodiment, the poly(meth)acrylate has a polydispersity in the range of from about 1.5 to about 5.0. In an even more preferred0 embodiment, the poly(meth)acrylate has a polydispersity in the range of from about 1.5 to about 3.0.
  • the polyisocyanate compound of the coating composition includes one or more cross-linking agents having at least two isocyanate groups. Any of the conventional aromatic, aliphatic, cycloaliphatic, isocyanates, 5 trifunctional isocyanates, and isocyanate functional adducts of a polyol and a diisocyanate can be used.
  • diisocyanates are 1 ,6- hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-biphenylene diisocyanate, toluene diisocyanate, bis cyclohexyl diisocyanate, tetramethylene xylene diisocyanate, ethyl ethylene diisocyanate, 2,3-0 dimethyl ethylene diisocyanate, 1-methyltrimethylene diisocyanate, 1 ,3- cyclopentylene diisocyanate, 1 ,4-cyclohexylene diisocyanate, 1 ,3- phenylene diisocyanate, 1 ,5-naphthalene diisocyanate, bis-(4- isocyanatocyclohexyl)-methane, and 4,4'-diisocyanatodiphenyl ether.
  • Typical trifunctional isocyanates include triphenylmethane5 triisocyanate, 1 ,3,5-benzene triisocyanate, and 2,4,6-toluene triisocyanate. Trimers of diisocyanates also can be used, such as the trimer of hexamethylene diisocyanate, which is supplied by Bayer Corp., Pittsburgh, Pa., under the trademark Desmodur ® N 3300A. Other suitable polyisocyanates from Bayer Corp. include Desmodur ® N 3390A BA/SN0 and Z 4470BA polyisocyanates.
  • the relative amount of cross-linking agent used in the coating composition is adjusted to provide a molar equivalent ratio of NCO/(OH+NH) in the range of from about 0.5 to about 5, preferably in the 3, and more preferably in the range of from about 0.85 to about 2.
  • the coating composition is suitable for use as a clear or pigmented composition.
  • the coating composition can be used as a monocoat, as a 5 basecoat, or as a primer.
  • the coating composition can include additional components such as solvents, catalysts, pigments, fillers, and conventional additives.
  • the suitable solvents include aromatic hydrocarbons, such as petroleum naphtha or xylenes; esters, such as, butyl acetate, t-butyl 0 acetate, isobutyl acetate or hexyl acetate; and glycol ether esters, such as propylene glycol monomethyl ether acetate.
  • aromatic hydrocarbons such as petroleum naphtha or xylenes
  • esters such as, butyl acetate, t-butyl 0 acetate, isobutyl acetate or hexyl acetate
  • glycol ether esters such as propylene glycol monomethyl ether acetate.
  • the amount of organic solvent added depends upon the desired solids level as well as the desired amount of VOC of the composition. If desired, the organic solvent may be added to both the components of the coating composition. 5
  • the coating composition preferably includes a catalytic amount of a catalyst for accelerating the curing process.
  • catalysts can be used, such as tin compounds, including dibutyl tin dilaurate and dibutyl tin diacetate and tertiary amines such as triethylenediamine. These catalysts can be used alone or in conjunction with carboxylic acids, such as acetic acid.
  • One of the commercially 5 available catalysts sold under the trademark Fastcat ® 4202 dibutyl tin dilaurate (Elf-Atochem North America, Inc., Philadelphia, Pa.), is particularly suitable. Hydrolyzing the protective group leads to the recovery of the original poly(meth)acrylate with hydroxyl groups available for cross-linking.0 Hydrolysis can occur in water, optionally in the presence of an acid catalyst.
  • Suitable acids include acetic acids and the like, phosphorous and phosphoric acids and their esters, hydrochloric acid, perchloric acid, hydrobromic acid, sulfuric acid and its half-esters, sulfonic SPy decjSyrlSrlisulfonic acid, and compounds that generate acids upon hydrolysis such as, for example, POCI 3 , SOCI 2 , and PCI .
  • the hydrolysis reaction can occur before or concurrently with the addition of cross-linker.
  • the blocked poly(meth)acrylates are unblocked, and the hydroxyl groups thus recovered, concurrently with the addition of cross-linker.
  • the water may be introduced in a variety of ways.
  • the water may be introduced into the uncross-linked or cross-linking (while the cross-linking is taking place) coating by absorption from the air. Absorption is very convenient for making an uncross-linked coating composition that is stable until exposed to (moist) air.
  • water may be mixed in a mixing head or spray-mixing head (for a coating) just before cross-linking is to take place.
  • the coating composition can contain one or more coloring or special effect producing pigments.
  • inorganic or organic coloring pigments include titanium dioxide, micronized titanium dioxide, iron oxide pigments, carbon black, azo pigments, phthalocyanine pigments, quinacridone pigments, and pyrrolopyrrol pigments.
  • special effect producing pigments include aluminum flake, copper bronze flake, and other metal flakes; interference pigments such as, for example, metal oxide coated metal pigments, for example, titanium dioxide coated or mixed oxide coated aluminum, coated mica such as, for example, titanium dioxide coated mica and graphite special effect pigments.
  • fillers include silicon dioxide, aluminium silicate, barium sulfate, and talcum.
  • the coating composition may also include conventional additives such as wetting agents; leveling and flow control agents, for example, BYK ® 320 and 325 (high molecular weight polyacrylates; BYK-Chemie USA Inc., Wallingford, Conn.), BYK ® 347 (polyether-modified siloxane), and BYK ® 306 (polyether-modified dimethylpolysiloxane); rheology control IP li:: defoamers; surfactants; and emulsifiers to help stabilize the composition.
  • Other additives that tend to improve mar resistance can be added, such as silsesquioxanes and other silicate- based micro-particles.
  • Such additional additives will, of course, depend on 5 the intended use of the coating composition. Any additives that would adversely affect the clarity of the cured coating will not be included when the composition is used as a clear coating.
  • the foregoing additives may be added to either component or both depending upon the intended use of the coating composition.0
  • from about 0.1 to about 5 weight percent, preferably from about 0.5 to about 2.5 weight percent, and more preferably from about 1 to about 2 weight percent of ultraviolet light stabilizers screeners, quenchers, and antioxidants can be added to the composition, the percentages being based on the total weight of the binder5 and cross-linking components solids.
  • Typical ultraviolet light screeners and stabilizers include the following: Benzophenones such as hydroxy dodecycloxy benzophenone, 2,4- dihydroxy benzophenone, and hydroxy benzophenones containing sulfonic acid groups.0 Benzoates such as dibenzoate of diphenylol propane and tertiary butyl benzoate of diphenylol propane.
  • Triazines such as 3,5-dialkyl-4-hydroxyphenyl derivatives of triazine and sulfur containing derivatives of dialkyl-4-hydroxy phenyl triazine and hydroxy phenyl-1 ,3,5-triazine.5 Triazoles such as 2-phenyl-4-(2,2'-dihydroxy benzoyl)-triazole and substituted benzotriazoles such as hydroxy-phenyltriazole.
  • Hindered amines such as bis(1 ,2,2,6,6-entamethyl-4-piperidinyl sebacate) and di[4(2,2,6,6-tetramethyl piperidinyl)]sebacate; and any mixtures of any of the above.0
  • the hydrolyzable ketal group has the following chemical structure: wherein Ri is an alkyl substituent of 1 to 6 carbon atoms; and R 2 and R 3 are, independently, alkyl substituents of 1 to 6 carbon atoms or cyclic substituents of 4 to 7 carbon atoms.
  • the invention concerns a process for curing coating composition
  • a process for curing coating composition comprising thermally reacting a poly(meth)acrylate containing at least two hydroxyl groups with at least one vinyl ether compound, hydrolyzing the product of the thermal reaction step to unblock the poly(meth)acrylate containing at least two hydroxyl groups, and reacting the unblocked poly(meth)acrylate containing at least two hydroxyl groups with at least one polyisocyanate compound.
  • the at least one vinyl ether compound has the following chemical structure:
  • Ri is an alkyl substituent of 1 to 6 carbon atoms
  • R 3 is an alkyl substituent of 1 to 6 carbon atoms or a cyclic substituent of 4 to 7 carbon atoms including carbon atoms of the double bond
  • R is hydrogen, an alkyl substituent of 1 to 6 carbon atoms, or a cyclic substituent of 4 to 7 carbon atoms including carbon atoms of the double bond.
  • the at least one vinyl ether compound is 2-methoxypropene.
  • the blocking reaction occurs through acid catalysis. To block the hydroxyl groups of a poly(meth)acrylate compound, the poly(meth)acrylate is reacted with an excess of a vinyl ether compound in presence of an acid catalyst.
  • Suitable acid catalysts include any of those listed above.
  • the hydroxyl groups are blocked, for example, by the following reaction: wherein R ⁇ ⁇ is an alkyl substituent of 1 to 6 carbon atoms; R 2 is an alkyl substituent of 1 to 6 carbon atoms or a cyclic substituent of 4 to 7 carbon atoms; R 3 is an alkyl substituent of 1 to 6 carbon atoms or a cyclic substituent of 4 to 7 carbon atoms including carbon atoms of the double bond; and R is hydrogen, an alkyl substituent of 1 to 6 carbon atoms, or a cyclic substituent of 4 to 7 carbon atoms including carbon atoms of the double bond.
  • Polyol represents the poly(meth)acrylate backbone.
  • coatings of the invention can comprise at least one of a spiroorthocarbonate compound and an amide acetal compound.
  • Spiroorthocarbonate compounds are described in co- pending, co-owned application Serial No. 60/261 ,450, and amide acetal compounds are described in co-pending, co-owned application Serial No. 60/509,885.
  • the spiroorthocarbonate compound has the following chemical structure:
  • R 5 and R 6 are, independently, hydrocarbylene or substituted hydrocarbylene bridging groups that have at least two bridging carbon atoms. It is preferred that there independently be 2 or 3 atoms in each bridge between oxygen atoms.
  • hydrocarbylene is meant a group containing only carbon and hydrogen that has two free valences to carbon atoms, and both free valences are not to the same carbon atom.
  • one or more hydrogen atoms are substituted for by a functional group that does not interfere with the desired reactions of, or the formation of, the compound involved. Suitable functional groups include halo, ether including alkoxy, hydroxyl, etc.
  • R 5 and R 6 each independently have the formula -CR 7 R 8 -CR 9 R ⁇ o-(CR ⁇ R ⁇ 2 ) n -, wherein n is 0 or 1 , and each of R - R ⁇ 2 independently is hydrogen, hydrocarbyl, or substituted hydrocarbyl, provided that any two of R 7 -R- ⁇ 2 vicinal or geminal to each other taken together may form a ring.
  • R and R 6 are the same.
  • Independently preferred groups for R -R ⁇ 2 are hydrogen; alkyl, especially alkyl containing 1 to 10 carbon atoms, more preferably methyl or ethyl; and hydroxyaklyl, especially hydroxymethyl. Substitution patterns for specific preferred compounds are given in Table 1.
  • the amide acetal compound has the following chemical structure:
  • R ⁇ 3 -R 2 ⁇ are, independently, hydrogen, Ci to C 22 alkyl, Ci to C 20 alkenyl, C-i to C 20 alkynyl, Ci to C 20 aryl, Ci to C 20 alkyl ester, or Ci to C 20 p alkynyl, aryl, or aralkyl each optionally having at least one substituent selected from the group consisting of halo, alkoxy, nitro, amino, alkylamino, dialkylamino, cyano, alkoxy silane and amide acetal (difunctional), and carbamoyl.
  • coatings of this invention can comprise at least one of a conventional acrylic polymer, a polyester, a reactive oligomer, a dispersed acrylic polymer, an aldimine or ketimine, and a polyaspartic ester.
  • the conventional acrylic polymer suitable for use in the present 0 invention can have a GPC Mw exceeding 5,000, preferably in the range of from 5,000 to 20,000, more preferably in the range of 6,000 to 20,000, and most preferably in the range of from 8,000 to 12,000.
  • the T g of the acrylic polymer varies in the range of from 0°C to 100°C, preferably in the range of from 30°C to 80°C.
  • the acrylic polymer suitable for use in the present invention can be conventionally polymerized from typical monomers, such as alkyl (meth)acrylates having alkyl carbon atoms in the range of from 1 to 18, preferably in the range of from 1 to 12, and styrene and functional monomers such as hydroxyethyl acrylate and hydroxyethyl methacrylate.
  • the polyester suitable for use in the present invention can have a GPC Mw exceeding 1 ,500, preferably in the range of from 1 ,500 to 100,000, more preferably in the range of 2,000 to 50,000, still more preferably in the range of 2,000 to 8,000, and most preferably in the range of from 2,000 to 5,000.
  • the T g of the polyester varies in the range of from 5 -50°C to 100°C, preferably in the range of from -20°C to 50°C.
  • Suitable polyesters can be conventionally polymerized from suitable polyacids, including cycloaliphatic polycarboxylic acids, and suitable polyols, which include polyhydric alcohols.
  • Suitable cycloaliphatic polycarboxylic acids are tetrahydrophthalic acid,0 hexahydrophthalic acid, 1 ,2-cyclohexanedicarboxylic acid, 1 ,3- cyclohexanedicarboxylic acid, 1 ,4-cyclohexanedicarboxylic acid, 4- methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, tricyclodecanedicarboxylic acid, endoethylenehexahydrophthalic acid, camphoric acid, cyclohexanetetracarboxylic acid, and acid.
  • the cycloaliphatic polycarboxylic acids can be used not only in their cis but also in their trans form and as a mixture of both forms.
  • suitable polycarboxylic acids which, if desired, can be used together with the cycloaliphatic polycarboxylic acids, are aromatic and aliphatic polycarboxylic acids, such as, for example, phthalic acid, isophthalic acid, terephthalic acid, halogenophthalic acids, such as, tetrachloro- or tetrabromophthalic acid, adipic acid, glutaric acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, trimellitic acid, and pyromellitic acid.
  • Suitable polyhydric alcohols include ethylene glycol, propanediols, butanediols, hexanediols, neopentylglycol, diethylene glycol, cyclohexanediol, cyclohexanedimethanol, trimethylpentanediol, ethylbutylpropanediol, ditrimethylolpropane, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, tris(hydroxyethyl) isocyanate, polyethylene glycol, and polypropylene glycol.
  • monohydric alcohols such as, for example, butanol, octanol, lauryl alcohol, ethoxylated, or propoxylated phenols may also be included along with polyhydric alcohols.
  • polyester suitable for use in the present invention are further provided in the U.S. Patent No. 5,326,820.
  • One commercially available polyester, which is particularly preferred, is SCD ® -1040 polyester, which is supplied by Etna Products Inc., Chagrin Falls, Ohio.
  • Useful reactive oligomers are covered in U.S. Patent No. 6,221 ,494. Non-alicyclic (linear or aromatic) oligomers can also be used, if desired.
  • non-alicyclic-oligomers can be made by using non-alicyclic anhydrides, such as succinic or phthalic anhydrides, or mixtures thereof.
  • Caprolactone oligomers described in U.S. Patent No. 5,286,782 can also be used.
  • Typical useful dispersed acrylic polymers are prepared by dispersion polymerizing at least one vinyl monomer in the presence of a polymer dispersion stabilizer and an organic solvent.
  • the polymer dispersion stabilizer may be any of the known stabilizers used commonly in the field of dispersed acrylic polymers. These dispersed acrylic polymers are covered in U.S. Patent No. 5,763,528.
  • pc ⁇ :/ ⁇ (table al ⁇ fm ⁇ rife ⁇ :; may be prepared from aldehydes such as acetaldehyde, formaldehyde, propionaldehyde, isobutyraldehyde, n- butyraldehyde, heptaldehyde, and cyclohexyl aldehydes by reaction with amine.
  • aldehydes such as acetaldehyde, formaldehyde, propionaldehyde, isobutyraldehyde, n- butyraldehyde, heptaldehyde, and cyclohexyl aldehydes by reaction with amine.
  • Representative amines that may be used to form the aldimine 5 include ethylene diamine, ethylene triamine, propylene diamine, tetramethylene diamine, 1 ,6-hexamethylene diamine, bis(6- aminohexyl)ether, tricyclodecane diamine, N.N'-dimethyldiethyltriamine, cyclohexyl-1 ,2,4-triamine, cyclohexyl-1 ,2,4,5-tetraamine, 3,4,5- triaminopyran, 3,4-diaminofuran, and cycloaliphatic diamines.
  • Suitable polyaspartic esters are typically prepared by the reaction of diamines such as isophorone diamine with dialkyl maleates such as diethyl maleate.
  • diamines such as isophorone diamine
  • dialkyl maleates such as diethyl maleate.
  • Suitable ketimines are typically prepared by the reaction of ketones with amines.
  • Representative ketones, which may be used to form the ketimine, include acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diethyl ketone, benzyl methylketone, diisopropyl 0 ketone, cyclopentanone, and cyclohexanone.
  • Representative amines which may be used to form the ketimine include ethylene diamine, ethylene triamine, propylene diamine, tetramethylene diamine, 1 ,6- hexamethylene diamine, bis(6-aminohexyl)ether, tricyclodecane diamine, N.N'-dimethyldiethyltriamine, cyclohexyl-1 ,2,4-triamine, cyclohexyl-1 ,2,4,5- 5 tetraamine, 3,4,5-triaminopyran, 3,4-diaminofuran, and cycloaliphatic diamines.
  • Preparation and other suitable imines are shown in U.S. Patent No. 6,297,320.
  • the invention concerns a process for coating a substrate comprising applying a base coat to the substrate, 0 applying a clear coat over the base coat wherein the clear coat comprises a poly(meth)acrylate containing at least two hydroxyl groups blocked by hydrolyzable ketal groups and at least one polyisocyanate compound, hydrolyzing the ketal groups of the poly(meth)acrylate containing at least two hydroxyl groups, and cross-linking the unblocked poly(meth)acrylates reaction with at least one polyisocyanate compound.
  • the coating composition can be supplied in the form of a two-pack coating composition.
  • the cross-linkable component and the cross-linking component are mixed, typically just prior to application to form a pot mix.
  • the mixing can take place though a conventional mixing nozzle or separately in a container.
  • a layer of the pot mix generally having a thickness in the range of 15 ⁇ m to 200 ⁇ m is applied over a substrate, such as an automotive body or an automotive body that has precoated layers, such as electrocoat primer.
  • the foregoing application step can be conventionally accomplished by spraying, electrostatic spraying, roller coating, dipping, or brushing the pot mix over the substrate.
  • the layer after application is typically dried to reduce the solvent content from the layer and then cured at a temperature ranging from ambient to about 204°C. Under typical automotive original equipment manufacturer (“OEM”) applications, the dried layer of the composition can be typically cured at elevated temperatures ranging from about 60°C to about 160°C in about 10 to 60 minutes.
  • OEM automotive original equipment manufacturer
  • curing can take place at about ambient to about 60°C, and for heavy duty truck body applications, curing can take place at about 60°C to about 80°C.
  • the cure under ambient conditions occurs in about 30 minutes to 24 hours, generally in about 30 minutes to 4 hours, to form a coating on the substrate having the desired coating properties.
  • the actual curing time can depend upon the thickness of the applied layer, the cure temperature, humidity, and on any additional mechanical aids, such as fans, that assist in continuously flowing air over the coated substrate to accelerate the cure rate. It is understood that actual curing temperature would vary depending upon the catalyst and the amount thereof, thickness of the layer being cured, and the amount of the cross-linking component utilized.
  • the suitable substrates for applying the coating composition include automobile bodies; any and all items manufactured and painted by automobile sub-suppliers; frame rails; commercial trucks and truck bodies, including but not limited to beverage bodies, utility bodies, ready mix waste hauling vehicle bodies, and fire and emergency vehicle bodies, as well as any potential attachments or components to such truck bodies, buses, farm, and construction equipment; truck caps and covers; commercial trailers; consumer trailers; 5 recreational vehicles, including but not limited to, motor homes, campers, conversion vans, vans, pleasure vehicles, pleasure craft snow mobiles, all terrain vehicles, personal watercraft, motorcycles, boats, and aircraft.
  • the substrate further includes industrial and commercial new construction and maintenance thereof; cement and wood floors; walls of commercial and 0 residential structures, such office buildings and homes; amusement park equipment; concrete surfaces, such as parking lots and drive ways; asphalt and concrete road surface; wood substrates; marine surfaces; outdoor structures, such as bridges; towers; coil coating; railroad cars; printed circuit boards; machinery; OEM tools; signage; fiberglass 5 structures; sporting goods; and sporting equipment.
  • industrial and commercial new construction and maintenance thereof cement and wood floors; walls of commercial and 0 residential structures, such office buildings and homes; amusement park equipment; concrete surfaces, such as parking lots and drive ways; asphalt and concrete road surface; wood substrates; marine surfaces; outdoor structures, such as bridges; towers; coil coating; railroad cars; printed circuit boards; machinery; OEM tools; signage; fiberglass 5 structures; sporting goods; and sporting equipment.
  • the flask was flashed with nitrogen gas, and 75 ml of 2-methoxypropene was added. After 10 min. of stirring, 0.05 ml of phosphorous oxychloride was added. After 45 min. of stirring, 2 g of basic alumina was added. After 15 min. of stirring, the flask's contents were filtered and evaporated under 15 Torr vacuum at 60 °C to remove all volatile components. After 1 hr., the flask was filled with nitrogen, and its contents were transferred to an airtight container. IR Spectrum of the mixture showed no significant signal from hydroxyl groups in the 3,100- 3,300 cm "1 region.
  • Ketal Composition A Coatings using Ketal Composition A
  • a glass container 26.76 g of Ketal Composition A was combined with 7.15 g of propylene glycol monomethylether acetate, 2.16 g of a 2% dibutyl tin dilaurate solution in ethyl acetate, and 1.1 g of a 10% BYK ® 306 solution (polyether-modified dimethylpolysiloxane; Byk-Chemie) in xylene. 5
  • Desmodur ® N 3300A hexamethylene diisocyanate trimer; Bayer Corp.
  • the third, Coating C contained ketal-protected HEMA/IBOA (in the form of Ketal Composition B).
  • HEMA/IBOA in the form of Ketal Composition B.
  • All three coatings contained a spiroorthocarbonate component (3,9-dibutyl-3,9-diethyl-1 ,5,7,11-tetraoxaspiro[5,5]undecane) as described in Experiment 2 of co-pending, co-owned application Serial No. 60/261 ,450, wherein 2-ethyl-1 ,3-hexanediol replaces 2-butyl-2-ethyl- 1 ,3-propanediol.
  • Table 2
  • the three coating compositions were tested for viscosity, cotton tack free time, BK3 time, and water spot rating. Gardner-Holt viscosity was measured under ASTM test D1545.
  • a coated panel is allowed to dry for a set period of time (for example, 30 min.).
  • a cotton ball is dropped from a height of 2.5 cm onto the surface of the panel, and the cotton ball is left on the surface for a set time interval (for example, intervals of 30 min.).
  • the panel is then inverted. These steps are repeated until the cotton ball drops off the panel on inversion (that is, the cotton tack free time).
  • the dry time of a coated layer of the composition was measured as BK3 surface dry time under ASTM test D5895.
  • Water spot rating is a measure of how well the coating composition is cross-linked early in the curing of the coating composition. Water spot damage on the coating composition indicates that the cure is not complete S ⁇ composition is needed before the coating composition can be wet sanded, buffed, or moved from the spray booth.
  • the water spot rating is determined as follows. Panels coated with the test coating compositions were laid on a flat surface and deionized water was applied with a pipette at 1 hr. timed intervals. A drop of about 1.25 cm in diameter was placed on the panel and allowed to evaporate. The spot on the panel was checked for deformation and discoloration. The panel was wiped lightly with cheesecloth wetted with deionized water followed by lightly wiping the panel dry with the cloth.
  • the panel was then rated on a scale of 1 to 10.
  • a rating of 10 is best - no evidence of spotting or distortion of discoloration; rating 9 - barely detectable; rating 8 - slight ring; rating 7 - very slight discoloration or slight distortion; rating 6 - slight loss of gloss or slight discoloration; rating 5 - definite loss of gloss or discoloration; rating 4 - slight etching or definite distortion; rating 3 - light lifting, bad etching, or discoloration; rating 2 - definite lifting; and rating 1 - dissolving of the coating composition.
  • Table 5 shows the cure improvement found in Coating C because of the addition of the ketal group (Ketal Composition B) compared to Coating A without substantially harming potlife.
  • Coating B versus Coating C is a comparison of the unprotected material (B) versus protected material (C). Coating C has better potlife at equal solids (75%) with similar cure.
  • Table 5 shows the cure improvement found in Coating C because of the
  • EXAMPLE 7 For each of the coating compositions D-E, Portions 1 , 2, and 3 were mixed together to form the coating composition as shown in Table 6. Each of the coating compositions was applied with a doctor blade over a separate phosphated cold roll steel panel primed with a layer of PowerCron ® Primer supplied by PPG, Pittsburgh, Pa., to a dry coating thickness of 50 ⁇ m, and air dried at ambient temperature conditions. Table 6
  • BYK '20% BYK 301 flow additive in propylene glycol monomethyl ether acetate supplied by BYK-Chemie 2 1% di butyl tin dilaurate in methyl ethyl ketone supplied by Elf-Atochem North America, Inc (Philadelphia, Pa ) 3 lsocyanurate trimer of hexamethylene diisocyanate supplied by Rhodia, Inc (Cranbury, N J ) Aromatic Sulfonic acid, Nacure ® XP-211 in isopropanol supplied by King Industries The coating compositions were tested for BK3 time, BK4 time, water spot rating, Persoz Hardness, Fischer Hardness, MEK solvent resistance, viscosity, and time to gel.
  • Example 5 BK3 time and water spot rating tests were performed as described in Example 5.
  • the dry time of a coated layer of the composition was also measured as BK4 surface dry time under ASTM test D5895.
  • the change in film hardness (Persoz Hardness) of the coating was measured with respect to time by using a Persoz hardness tester Model No. 5854 (ASTM D4366), supplied by Byk-Mallinckrodt, Wallingford, Conn.
  • the number of oscillations (referred to as Persoz number) was recorded. I O ⁇ t-_-l ⁇ ⁇ ⁇
  • Comparing coatings D to E shows the significant advantages of using polymers with protected hydroxyl groups over the use of more conventional acrylics with hydroxyl groups in coatings.
  • Coating E has significantly lower viscosity and longer time to gel than coating D with comparable cure.

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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
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  • Wood Science & Technology (AREA)
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Abstract

L'invention concerne une composition de revêtement dans laquelle des groupes cétal bloquent des groupes hydroxyle de poly(méth)acrylate et des groupes cétal pouvant être éliminés par hydrolyse afin de faciliter la réticulation lors de la réaction avec des composés de polyisocyanate. L'invention concerne également un procédé destiné à durcir la composition de revêtement susmentionnée. Elle concerne aussi un procédé destiné à revêtir des substrats sur lequel un enduit lustré contenant la composition de revêtement susmentionnée est revêtue sur une couche de fond. L'invention concerne enfin un procédé destiné à bloquer des groupes hydroxyle d'un composé de poly(méth)acrylate par réaction avec un composé cétal.
PCT/US2005/008888 2004-03-22 2005-03-16 Polyols proteges par du cetal destines a des revetements a faible teneur en contaminant organique volatil (cov) WO2005092976A1 (fr)

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WO2004090056A1 (fr) * 2003-04-04 2004-10-21 E.I. Dupont De Nemours And Company Compositions reticulables polymeres contenant des amides acetals

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US5003004A (en) * 1986-04-18 1991-03-26 E. I. Du Pont De Nemours And Company Tough flexible polymer blends
US5241002A (en) * 1990-06-08 1993-08-31 Dainippon Ink And Chemicals, Ltd. Anionic living polymers, their derivatives and composition comprising them
US5571884A (en) * 1994-11-18 1996-11-05 Arco Chemical Technology, L.P. Hydroxy-functional acrylate resins

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US4596853A (en) * 1985-02-19 1986-06-24 Ashland Oil, Inc. Reactive polymer solutions and polymerizates thereof
EP0295209A3 (fr) * 1987-06-10 1990-01-24 Ciba-Geigy Ag Esters d'acide orthocarbonique
DE4024204A1 (de) * 1990-07-31 1992-02-06 Basf Lacke & Farben Ueberzugsmittel auf der basis hydroxylgruppen enthaltender polykondensations- und polyadditionsprodukte sowie deren verwendung
US5286782A (en) * 1992-08-31 1994-02-15 E. I. Du Pont De Nemours And Company Coating composition of an acrylic polymer, polyol and polyisocyanate crosslinking agent
US5763528A (en) * 1996-12-17 1998-06-09 E. I. Du Pont De Nemours And Company Coating compositions containing non-aqueous dispersed polymers having a high glass transition temperature
US6045870A (en) * 1997-09-03 2000-04-04 Kansai Paint Co., Ltd. High solid coating composition and method for forming topcoat using same
US6221494B1 (en) * 1998-11-03 2001-04-24 E.I. Du Pont De Nemours And Company Reactive oligomers for isocyanate coatings
ES2228176T3 (es) * 1998-11-20 2005-04-01 The Sherwin-Williams Company Composiciones curables que comprenden funcionalidad acetoacetoxi e imina.
US7129290B2 (en) * 2002-01-11 2006-10-31 E. I. Du Pont De Nemours And Company Polymeric crosslinkable compositions containing spiroorthocarbonates

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US5003004A (en) * 1986-04-18 1991-03-26 E. I. Du Pont De Nemours And Company Tough flexible polymer blends
US5241002A (en) * 1990-06-08 1993-08-31 Dainippon Ink And Chemicals, Ltd. Anionic living polymers, their derivatives and composition comprising them
US5571884A (en) * 1994-11-18 1996-11-05 Arco Chemical Technology, L.P. Hydroxy-functional acrylate resins

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